Anion−π Catalysis on Fullerenes

Lopez Andarias, Javier; Frontera, Antonio; Matile, Stefan

doi:10.1021/jacs.7b08113

Scientific article

English

Anion−π Catalysis on Fullerenes

Contributors

Lopez Andarias, Javier; Frontera, Antonio; Matile, Stefan

Published in

Journal of the American Chemical Society, vol. 139, no. 38, p. 13296-13299

Publication date

2017

Abstract

Anion−π interactions on fullerenes are about as poorly explored as the use of fullerenes in catalysis. However, strong exchange-correlation contributions and the localized π holes on their surface promise unique selectivities. To elaborate on this promise, tertiary amines are attached nearby. Dependent on their positioning, the resulting stabilization of anionic transition states on fullerenes is shown to accelerate disfavored enolate addition and exo Diels–Alder reactions enantioselectively. The found selectivities are consistent with computational simulations, particularly concerning the discrimination of differently planarized and charge-delocalized enolate tautomers by anion−π interactions. Enolate−π interactions on fullerenes are much shorter than standard π–π interactions and anion−π interactions on planar surfaces, and alternative cation−π interactions are not observed. These findings open new perspectives with regard to anion−π interactions in general and the use of carbon allotropes in catalysis.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

UNIGE research groups

Groupe Matile

Citation (ISO format)

LOPEZ ANDARIAS, Javier, FRONTERA, Antonio, MATILE, Stefan. Anion−π Catalysis on Fullerenes. In: Journal of the American Chemical Society, 2017, vol. 139, n° 38, p. 13296–13299. doi: 10.1021/jacs.7b08113

Article (Published version)

Article (Accepted version)

Identifiers

PID : unige:97267
DOI : 10.1021/jacs.7b08113

Journal ISSN

0002-7863

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186downloads

Creation

02/10/2017 09:15:00

First validation

02/10/2017 09:15:00

Update

13/10/2025 19:45:39

Status update

15/03/2023 02:05:06

Last indexation

02/11/2025 20:18:53

Anion−π Catalysis on Fullerenes

Contributors

Published in

Publication date

Abstract

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

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Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation